Our invention relates to trimethyl and dimethylmethylene propyl polyhydropyran derivatives and processes for preparing mixtures of trimethyl and dimethylmethylene propyl polyhydropyrans as well as perfumery uses of such trimethyl and dimethylmethylene propyl polyhydropyran derivatives and process intermediates for such process including the compounds having the structures: ##STR4## wherein X is chloro or bromo.
There has been considerable work performed relating to substances which can be used to impart (or enhance) fragrances to (or in) various consumable materials including perfume compositions, colognes and perfumed articles such as solid or liquid anionic, cationic, nonionic or zwitterionic detergents, fabric softeners and cosmetic powders. These substances are used to diminish natural materials some of which may be in short supply and to provide more uniform properties in the finished product.
Winey, chamomile, juniper, sage, citrusy, spicy, pineapple, green and floral aromas with natural rose, tobacco-like and animalic undertones are particularly desirable in perfume compositions.
Chemical compounds having the pyran ring are known to be useful in flavor and fragrance compositions. Thus, published Japanese Application 74/011073 (Mar. 14, 1974) Mitsui Toatsu Chemicals Inc. discloses 2,5 diethyl tetrahydropyran-containing perfumes having rose-like aromas and good stability in air, sunlight and humidity.
U.S. Pat. No. 2,422,648 at column 5, lines 34-55 states:
"The unsaturated cyclic ethers prepared by the process of the invention are useful as diluents, modifying agents, and processing reagents in the textile industry, and the higher members particularly are valuable as solvents. They may also be used as reagents and/or additives in the formation of synthetic resins, plastics and synthetic rubbers and the higher members may serve as insecticides, fungicides, parasiticides or as constituents of insecticidal, fungicidal and parasiticidal compositions, etc. In addition, they are valuable intermediates in the syntheses of valuable organic products; for example, the substituted dihydropyrans may be hydrogenated, if desired, in the presence of a suitable hydrogenation catalyst such as Raney nickel, to produce a novel substituted tetrahydropyran compounds having the formula: ##STR5## (wherein the R's represent hydrogen or non-olefinic hydrocarbon)." PA1 "green, herbaceous, sweet, oily, slightly minty aroma with "pickled" green olive topnotes" (column 8, lines 10-15)".
Williams, et al, J. Am. Chem. Soc., 72, 5738-43 (1950) sets forth the following reaction sequence: ##STR6##
Hinnen, et al, Bull. Soc. Chim. France, 1964 (7), pages 1492-8 discloses the mixture of compounds defined according to the structure: ##STR7## which is in fact a mixture of the compounds, to wit: ##STR8## but does not show their organoleptic properties or their usefulness in perfumery. Furthermore, Hinnen, et al does not infer that the mixture of compounds defined according to the structure: ##STR9## has any useful organoleptic properties or for that matter exists at all.
Hall, et al, U.S. Pat. No. 4,192,782 issued on Jan. 29, 1980 discloses the mixture of compounds defined according to the structure: ##STR10## wherein this mixture contains compounds having the structures: ##STR11## Hall, et al further discloses the perfumery properties of such a mixture, to wit:
Gramenitakaya, et al, Zh. Org. Khim., 1975, 11(5), pages 990-5 discloses production of the compound having the structure: ##STR12## but not the mixture of compounds defined according to the structure: ##STR13## The Gramenitakaya, et al reference discloses the reactions: ##STR14##
Nothing in the prior art discloses a method for preparation of the genus of compounds defined according to the structure: ##STR15## or of the compound having the structure: ##STR16## and nothing in the prior art discloses the unexpected, unobvious and advantageous organoleptic properties of the mixture of compounds defined according to the structure: ##STR17## or the compound having the structure: ##STR18## which, in fact, is a mixture of compounds having the structures: ##STR19##